Preparation of trimethyl lead acetylides



United States Patent Patented Sept. 14-, 1965 3,206,490 PREPARATION OFTRZMETHYL LEAD ACETYLIDES Peter Ballinger, San Rafael, Califi, assignorto California Research Corporation, San Francisco, Calif a corpo- 5ration of Delaware 0 Drawing. Original application Sept. 7, 1961, Ser.No. 136,457. Divided and this application July 30, 1962, Ser. No.213,160

1 Claim. (Cl. 260437) This application is a division of co-pendingapplication Serial No. 136,457, filed September 7, 1961.

This invention relates to position. More particularly,

of even higher octane number.

Many materials have been added to the gasoline base stocks,

wild detonating side reactions which cause the knock in the modern en-The hydrocarbon base fuel of the compositions according to the inventionare prepared by conventional refining and blending processes. Theynormally contain straight-chain parafiins, branched-chain parafiins,olefins, aromatics and naphthenes. Since straight-chain paratfins fuelboiling in the basoline boiling range. Generally described, such fuelshave an ASTM (D-86) distillation with initial boiling point of about F.and a final boil- Preferably the unleaded base fuel has a Researchoctane number of at least 85, as determined by the accepted CFR enginetest methods. Also, contains at least 20% by volume of aromatichydrocarbons. Less than 30% by volume able characteristics. The morepreferred hydrocarbon base fuels are those which contain from 20-60% byvolume aromatic hydrocarbons and from 030% by volume of olefinichydrocarbons. Most preferably, a gasoline having all-round desirablecharacteristics has aromatic hydrocarbons and about finic hydrocarbons.

For practical purposes, not more lead compound positions.

be present.

The following examples illustrate the preparation of propynyl trimethyllead and butynyl trimethyl lead in accordance with the invention. Unlessotherwise specified, the proportions are on a weight basis.

EXAMPLE 1 as Research Method D-908 in ASTM Manual of Engine Test Methodsfor Rating Fuels. According to this A solution of n-butyl lithium (0.2mol) in 200 cc. mixed pentane-hexane Was mixed with 250 ml. of diethylether method the octaile numbers are also deslgnated 1L1 Octane Numbers.

1n a l-liter, 3-necked flask fitted with a reflux condenser, The tablealso Shows the effects on Octane number of stirrer and gas inlet tube.This solution was cooled in 5 h I ice, stirred, and methyl acetylene(propyne) was bubbled thebbase by 3 3 propyilllyl methyl through. Awhite suspension of propynyl lithium rapidly or utyny g i Y1 leaaccordmg t ,ii i O formed. As soon as evolution of heat ceased,indicating Egg. M i:3 ff g gziaf completion of the reaction, the passageof the gas was 1S as stopped. 57.6 g 02 mol) of trimethyl lead chloride10 9 and 18 mm strmgemthanhe .Research Mt It was then added to thesuspension and the mixture was Illustrates more .acmrately P demable 9of the heated. Since both reactants have a low solubility in i f g g ofth gf' ether 100 ml. of clioxane was added to improve the solu- 0t anmet 0 e composulons p en 6 to give the customary lead concentrationequivalent to bility, and the heating Was continued for 3 to 4 hours. '1The mixture was left overnight and the ether was removed gggit gl fi iThe data of the examples are Preby stripping under a vacuum. The residuewas distilled at 100 C. under a pressure of 40 mm. of mercury with TableI.--Octane numbers of gasoline with alkynyl trithe addition of a smallamount of mineral oil to assist the methyl leads final removal of thedistillate. Most of the dioxane and lead compound were collected in anice-cooled trap, and the ether was condensed in a Dry Ice trap. Thematerial in the ice-cooled trap was fractionated to remove dioxaneCompound Cone, Base Gasoline gJgal.

. which distilled at 28 C. under a pressure of 45 mm. of F4 p2 mercury,and the residue distilled entirely at 65.5 C. fi under a pressure of 16mm. of mercury. The product 25 propynyl TrgmethylLeain 0 premium 96,5825 was a colorless liquid (density, 1.82 g./ ml. at 23 C.) hav- 3 gginggood thermal stability. The yield was 15.8 g. corre- D g esponding to27%. The infra-red spectrum showed a 45 9 slrong absorption p M2130 r wth -c c l5t.ffifi iff f??i:::: 2.75 ifififfiiiiI: 133:? iii stretchingfrequency. The bond is alpha to the lead EXAMPLE 2 heplane' 4.6 g. (0.2mol) of sodium chips were added gradually The examples li abovetable.sl.mw that to 250 cc. of mechanically stirred liquid ammonia in agasohne.composmons of the mvertnon contammg suitable reaction vessel.Throughout the addition of the Pynyl mmethyl lead Or.butynyl tnmethyllead. are de- Sodium a Stream of gaseous ethyl acetylene (butyne 1)cidedly better on the basis of octane number ratings than wasintroduced. The blue color produced by the addicolzpambleunleadedlgasoln? z g t i tion of each piece of sodium was rapidlydischarged, and apparent y W1 6 y 1 0 men when all the sodium had beenused, a white suspension 40 thls Invention may one Sklned art wasobtained. 50.9 g. (0.176 mol) of trimethyl lead chloout dePartmg fromthe P P Qflhe P i ride wre added portionwise to this liquid and aVigorous it is to be understood that the invention is not l1m1ted toreaction occurred. Following this, 200 ml. of ethyl ether the Specificembodiments except as defined in the appended were added and the ammoniawas allowed to evaporate.

2; idler extract ifi gg and zg A r ii t hod of preparing alkynyltrimethyl lead which a y rous magnesium su a e. er remova o e ether,fractionation yielded 6 g. (11%) of a liquid boiling P K Passmg a 53 ilg il 9 at 54 C. at a pressure of 4 mm. of mercury. The infra- Sstmg O 3m 0 a C00 6 so u 0 a red Spectrum Showed a peak at 2130 cmfi due to thelower alkyl l1th1um 1n hydrocarbon solvent to form the stretching modeThe bond is alpha to the corresponding alkynyl lithium, thereafteradding to said lead-atom solution trimethyl lead chloride and dioxanesufficient to In further illustration of the superior new gasoline com-{naintah} said y y lithium a d trimethyl lead chloride position of theinvention, several compositions and tests f g m g g fiza 2:3 3? ifig g gthereon are given in the following additional examples. time y a g yThese tests show the improved effect of the combination 55 methyl leadfrom t e reaction 50 of the hydrocarbon base fuel with propynyltrimethyl lead or butynyl trimethyl lead as compared with fuels without1 References Cited by the Exammer lead compounds. UNITED STATES PATENTSThe following table is a summary of the pertinent data 2,356,476 8/44shappirio 26() 437 of the examples. The type of compositions of thehydro- 5 carbon base fuel is shown with respect to the normal oc- OTHERREFERENCES tane rating. The number is the clear octane rating of anBeermann et 211.: Z. fiir Anorg. and Alleg. Chemie, Band unleadedpremium and primary reference base gasolines. 276, pages 20-32 (pages20-24 principally relied on), This octane number, as already mentioned,is the accepted 1954.

Research octane number which is usually employed in designating a givengasoline. This method is described TQBIAS E- L V Prim ry Exammer.

atom. K Primary Reference Mixture: 2,2,4-trimethyl pentane; 20% n

